CN113644208B - PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same - Google Patents
PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same Download PDFInfo
- Publication number
- CN113644208B CN113644208B CN202110899504.1A CN202110899504A CN113644208B CN 113644208 B CN113644208 B CN 113644208B CN 202110899504 A CN202110899504 A CN 202110899504A CN 113644208 B CN113644208 B CN 113644208B
- Authority
- CN
- China
- Prior art keywords
- layer
- perovskite
- carbon
- pedot
- pss
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001721 carbon Chemical class 0.000 title claims abstract description 20
- 229920000144 PEDOT:PSS Polymers 0.000 title abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000031700 light absorption Effects 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000007731 hot pressing Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 230000005525 hole transport Effects 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using the same, and belongs to the technical field of perovskite solar cells. The solar cell device sequentially comprises a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer and a carbon electrode, wherein the solar cell device comprises the following components: the ethanol solution of PSS carries out modification treatment on the surface of the carbon electrode layer, so that the carbon surface is covered with a layer of PEDOT: PSS can effectively extract photo-generated holes of the perovskite active layer, enhance carrier separation and improve battery efficiency. In the preparation of the carbon electrode, the absolute ethyl alcohol is used for replacing an organic solvent in commercial conductive carbon slurry to promote the carbon film to fall off from the substrate, and a passivation layer material PEDOT is adsorbed on the carbon surface in the process: PSS, using PEDOT: the PSS has excellent hole extraction capability, improves the efficiency of the battery and enhances the long-term stability of the battery.
Description
Technical Field
The invention belongs to the technical field of perovskite solar energy electricity, and particularly relates to a PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using the same.
Background
With the continuous consumption of fossil energy, the human world faces two major problems of energy crisis and environmental pollution, and scientists around the world are looking for a new clean renewable energy to replace fossil energy. The clean renewable energy sources include wind energy, geothermal energy, tidal energy, biomass energy, solar energy and the like. The first three are greatly affected by regions, have limitations, have lower biomass energy utilization rate, immature technology and higher cost, and the solar energy is not limited by regions, is easy to use and has low cost. The solar energy is mainly utilized in a photoelectric conversion mode, and the solar cell is a device for converting light energy into electric energy, has the advantages of environmental protection, abundant resources, cleanness, reproducibility, low cost, small conversion limitation with electric energy and the like, has a very good prospect in practical application, and therefore, is widely attracting attention. Perovskite solar cells have become a research hotspot in society in recent years due to their high conversion efficiency, with the highest conversion efficiency having reached 25.5%. Conventional perovskite solar cells contain a hole transport layer and a metal electrode, and these electrode materials have many problems such as high cost and poor stability. Typical hole transport layer materials are Spiro-MeOTAD, P3HT, PTAA, etc., which are expensive and make the cell less stable. Noble metal electrodes, such as Au, are expensive and unsuitable for industrial production, ag is also a noble metal and is easily oxidized. The carbon material has the advantages of rich reserves, low cost, good work function matching and stability, and the like, and is an ideal substitute for the noble metal. The commercial conductive carbon paste purchased is DBE as a solvent, and the perovskite layer is easily damaged by the original solvent of the conductive carbon paste, so that the stability and the efficiency of the battery are poor. And the hole extraction capability of the carbon material itself is poor. PEDOT prepared by green solvent substitution: the PSS modified carbon electrode has good mechanical stability and strong hole extraction capability, and is in contact with the perovskite layer more tightly through a hot pressing process, so that the battery efficiency and stability are obviously improved.
Disclosure of Invention
The invention aims to provide a PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using the same. Commercial carbon slurries were prepared as PEDOT by a simple method: the PSS-modified carbon electrode was used as a counter electrode for perovskite solar cells, PEDOT: the passivation effect of the PSS can improve the hole extraction capability, and the hot pressing treatment can enable the counter electrode to be in better contact with the perovskite layer.
Based on the above purpose, the invention is realized by the following technical scheme:
PEDOT: the preparation method of the PSS modified carbon electrode comprises the following steps:
1) Blade coating commercial conductive carbon paste on common glass to form wet carbon film;
2) Immersing the wet carbon film in the solvent of PEDOT: soaking in absolute ethyl alcohol of PSS for 1-60 min, and performing PEDOT: PSS (1.3 wt% dispersion in H) 2 O, sigma-Aldrich) and absolute ethanol in a volume ratio of 1:1-20,
3) And (3) after the carbon film is removed from the glass, drying to obtain PEDOT: PSS-modified carbon electrode.
Specifically, a 3M tape was stuck on a common glass to control the thickness of the wet carbon film when the carbon film was knife coated, PEDOT: the volume ratio of PSS to absolute ethyl alcohol is 1:15, the soaking time of the carbon film in the ethyl alcohol is 1-30 minutes, the drying temperature is 70 ℃, and the drying time is 10 minutes.
Specifically, the primary solvent in the commercial conductive carbon paste is DBE, which is produced by Borun New Material technology Co.
PEDOT prepared by the preparation method: PSS-modified carbon electrode.
Using the aforementioned PEDOT: the perovskite solar cell is prepared from the PSS modified carbon electrode, and sequentially comprises a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer and a carbon electrode.
Further, the conductive substrate is an FTO, ITO or PET flexible base.
Further, the electron transport layer is made of TiO 2 Dense layer and TiO 2 Porous layer composition, the TiO 2 The thickness of the compact layer is 5-50 nm, and TiO 2 The thickness of the porous layer is 100-500 nm. TiO (titanium dioxide) 2 The preparation process of the compact layer is as follows: spin-coating 0.15M n-butanol solution of titanium acetylacetonate on a conductive substrate, and drying at 120-130 ℃ to obtain the conductive substrate;
TiO 2 the porous layer was prepared as follows: commercial TiO to be purchased 2 Slurry 18NRT and absolute ethanol by volumeDiluting according to the ratio of 1:6, and spin-coating on TiO 2 And (3) drying the compact layer at 120-130 ℃, and then sintering at 500 ℃ for 25-35 min to obtain the composite material.
Further, the perovskite light absorption layer is MAPbI 3 And the thickness of the perovskite light absorption layer film is 100-1000 nm. The perovskite light absorption layer is prepared as follows: 0.461g of PbI 2 0.159g MAI is dissolved in a mixed solution of 0.2mL of DMF and 0.8mL of DMF and stirred fully to obtain perovskite precursor solution, and the perovskite precursor solution is coated on TiO in a spin-on manner 2 And (3) on the porous layer, obtaining a perovskite precursor film, and annealing at 100 ℃ to obtain the perovskite precursor film.
Further, the carbon counter electrode is pressed on the perovskite layer through a hot pressing process.
Further, the carbon counter electrode is pressed on the perovskite layer through pressure of 0.3-1.2 MPa, and the hot pressing temperature is 50-150 ℃.
Further, the thickness of the carbon electrode layer is 5-50 μm. And a Spiro-OMeTAD hole transport layer is further arranged between the perovskite light absorption layer and the carbon counter electrode, and the thickness of the hole transport layer is 50-300 nm.
The invention has the following beneficial effects: the invention provides a simple method for obtaining a surface passivated carbon electrode. The perovskite battery prepared by the carbon electrode has better performance than the perovskite battery prepared by unused PEDOT: PSS passivated devices, especially photoelectric conversion efficiency and long term stability, are significantly improved, and the initial efficiency is still maintained at 94% when the devices are placed in an air environment for 30 days. This is due to this passage through PEDOT: in addition, the carbon electrode of the perovskite solar cell has stronger bending resistance and better contact with the light absorption layer.
Drawings
FIG. 1 is a schematic diagram of a carbon electrode perovskite solar cell;
FIG. 2 is a graph of the efficiency of the perovskite cell produced in example 1;
FIG. 3 shows the long term stability results of the perovskite cell made in example 1;
FIG. 4 is a graph of the efficiency of the perovskite cell produced in example 2;
FIG. 5 results of long term stability of perovskite cells made in example 2;
FIG. 6 is a graph of the efficiency of the perovskite cell produced in example 3;
FIG. 7 shows the long term stability results of perovskite cells prepared in example 3;
FIG. 8 is a graph of the efficiency of the perovskite cell produced in example 4;
fig. 9 long term stability results for perovskite cells made in example 4.
Detailed Description
The technical scheme of the present invention will be described in further detail with reference to specific embodiments and drawings, but the scope of the present invention is not limited thereto.
Example 1:
a preparation method of perovskite solar cell with carbon electrode as counter electrode comprises the following steps:
(1) Cleaning of FTO conductive substrates. Ultrasonically cleaning FTO glass with 10% detergent, acetone, glycol and deionized water at 480W power for 15min each, blow-drying with compressed air, and treating at room temperature in a plasma cleaner at 100W power for 15min to remove residual organic impurities and enhance wettability of the substrate to the solution;
(2) Compact TiO 2 Is prepared by the following steps. The precursor solution was a 0.15M n-butanol solution of titanium acetylacetonate. Sucking 80 mu L of precursor solution, dripping the precursor solution on the FTO in the step (1) to enable the solution to be paved on the whole surface of the FTO, spin coating at 4000rpm for 30s, and drying the precursor solution on a hot plate at 125 ℃ for 5min to obtain compact TiO with the thickness of 30nm 2 A layer;
（3）TiO 2 preparation of a porous layer. Commercial TiO to be purchased 2 Slurry 18NRT and absolute ethanol are diluted according to the volume ratio of 1:6. 80 mu L of the mixture is taken in TiO 2 Spin-coating the compact layer at 5000rpm for 30s, then drying the compact layer on a hot plate at 125 ℃ for 5min, and then sintering the compact layer at 500 ℃ for 30min to form a mesoporous electron transport layer with the thickness of 200 nm;
(4) And (3) preparing a perovskite light absorption layer. 0.461g of PbI 2 0.159g MAI was dissolved in a mixed solution of 0.2mL of DMF and 0.8mL of DMF and magnetically stirred for 8 hoursIn FTO/TiO 2 Dense layer/TiO 2 Dropwise adding 60 mu L of perovskite precursor solution on a substrate of the mesoporous layer, spin-coating for 20s at a rotating speed of 5000rpm to obtain a perovskite precursor film, and annealing on a hot plate at 100 ℃ for 30min to obtain a perovskite film with a thickness of 250 nm;
(5) And (3) preparing a carbon electrode layer. The commercial conductive carbon slurry (original solvent is DBE, purchased from Borun New Material technology Co., ltd.) is coated on clean common glass (2 layers of 3M adhesive tape are adhered on a glass plate, a long strip-shaped carbon film with the width of 1cm is formed in the middle), a carbon wet film is obtained, the carbon wet film is soaked in absolute ethyl alcohol for 30 minutes at room temperature, and after the carbon film is fallen off, the carbon film is transferred to a heating plate for heating for 10 minutes at the temperature of 70 ℃ to obtain a carbon electrode film with the thickness of 50 mu M;
(6) Cutting the carbon electrode film obtained in the step (5) into squares of 1cm x 1cm, and hot-pressing the squares on the perovskite film prepared in the step (4), wherein the hot-pressing conditions are as follows: hot-pressing at 80deg.C under 0.5MPa for 1min.
(7) And leading out the transparent conductive electrode and the carbon counter electrode to obtain the perovskite solar cell, and performing performance test, wherein the result is shown in figure 2. The cell efficiency was measured at room temperature under 1 standard simulated sunlight (AM 1.5) to be 12.86%. Short circuit current, open circuit voltage, and fill factor are respectively: 22.30mA/cm 2 ，0.95V，0.61。
(8) The stability test results are shown in figure 3. The cell was placed in dark conditions at a temperature of about 25 ℃ and atmospheric humidity of about 50%, maintaining 78% of the initial efficiency after 30 days.
Example 2:
one with PEDOT: the preparation method of the perovskite solar cell with the PSS modified carbon electrode as the counter electrode comprises the following steps:
(1) Cleaning of FTO conductive substrates. As in example 1;
(2) Compact TiO 2 Is prepared by the following steps. As in example 1;
（3）TiO 2 preparation of a porous layer. As in example 1;
(4) And (3) preparing a perovskite light absorption layer. As in example 1;
(5) And (3) preparing a carbon electrode layer. Commercial conductive carbon paste (original solvent is DBE, purchased from Borun New Material technology Co., ltd.) is coated on clean common glass (2 layers of 3M adhesive tape are adhered on a glass plate, a long strip-shaped carbon film with the width of 1cm is formed in the middle), so as to obtain a carbon wet film, and the carbon wet film is soaked in a solvent with PEDOT: and (3) putting PSS in absolute ethyl alcohol for 30 minutes (the volume ratio of PEDOT to PSS to absolute ethyl alcohol is 1:15), transferring the carbon film to a heating plate to 70 ℃ after the carbon film is removed, and heating for 10 minutes to obtain 50-mu m-thick PEDOT: PSS modified carbon electrode film;
(6) Cutting the carbon electrode film obtained in the step (5) into squares of 1cm x 1cm, and hot-pressing the squares on the perovskite film prepared in the step (4), wherein the hot-pressing conditions are as follows: hot-pressing at 80deg.C under 0.5MPa for 5min.
(7) And leading out the transparent conductive electrode and the carbon counter electrode to obtain the perovskite solar cell, and performing performance test, wherein the result is shown in figure 4. The cell efficiency was measured at room temperature under 1 standard simulated sunlight (AM 1.5) to be 13.62%. Short circuit current, open circuit voltage, and fill factor are respectively: 22.31mA/cm 2 ，0.98V，0.62。
(8) The stability test results are shown in fig. 5. The cell was placed in dark conditions at a temperature of about 25 ℃ and atmospheric humidity of about 50% maintaining 80% of the initial efficiency after 30 days.
As shown in FIG. 1, the perovskite solar cell prepared by the preparation method sequentially comprises an FTO conductive substrate, an electron transport layer, a perovskite layer and a carbon electrode layer from bottom to top, wherein the electron transport layer comprises TiO (titanium oxide) 2 Dense layer and TiO 2 The porous layers are sequentially spin-coated on the transparent conductive substrate, and the thickness of each layer can be changed by adjusting the spin-coating rotating speed or the spin-coating liquid dilution ratio. Wherein the TiO is 2 The thickness of the compact layer is 5-50 nm, and TiO 2 The thickness of the porous layer is 100-500 nm. The perovskite light absorption layer is CH 3 NH 3 PbI 3 And the thickness of the perovskite light absorption layer film is 100-1000 nm. The thickness of the carbon electrode layer is 5-50 mu m, and the thickness of the carbon electrode can be adjusted by adjusting hot pressing time or pressure.
Example 3:
one with PEDOT: the preparation method of the perovskite solar cell with the PSS modified carbon electrode as the counter electrode comprises the following steps:
(1) Cleaning of FTO conductive substrates. As in example 1;
(2) Compact TiO 2 Is prepared by the following steps. As in example 1;
（3）TiO 2 preparation of a porous layer. As in example 1;
(4) And (3) preparing a perovskite light absorption layer. As in example 1;
(5) The preparation of the hole transport layer comprises the following specific processes: 1mL chlorobenzene, 72.3mg Spiro-OMeTAD, 28.8. Mu.L 4-tertbutylpheno, 17.5. Mu.L Li-TFSI (acetonitrile as solvent) at a concentration of 520mg/mL were thoroughly mixed. Taking 70 mu L of hole transport layer solution, spin-coating the solution onto a perovskite light absorption layer at a rotating speed of 4000rpm for 30s, and placing the solution in dry air in a dark place for 8 hours to obtain a hole transport layer with a thickness of 150 nm;
(6) And (3) preparing a carbon electrode layer. Spreading commercial conductive carbon slurry (original solvent is DBE, purchased from Borun New Material technology Co., ltd.) on clean common glass (2 layers of 3M adhesive tape are adhered on a glass plate, and a long strip-shaped carbon film with the width of 1cm is formed in the middle), so as to obtain a carbon wet film, soaking the carbon wet film in absolute ethyl alcohol for 30 minutes at room temperature, transferring to a heating plate for heating at 70 ℃ for 10 minutes after the carbon film is fallen off, and obtaining a 50 μm carbon electrode film;
(7) Cutting the carbon electrode film obtained in the step (6) into squares of 1cm x 1cm, and hot-pressing the squares on the hole transport layer prepared in the step (4), wherein the hot-pressing conditions are as follows: hot-pressing at 80deg.C under 1 MPa for 1min.
(8) The transparent conductive electrode and the carbon counter electrode were led out to obtain a perovskite solar cell, and performance test was performed, and the results are shown in fig. 6. The cell efficiency was measured to be 15.03%. Short circuit current, open circuit voltage, and fill factor are respectively: 22.51mA/cm 2 ，1.04V，0.64。
(9) The stability test results are shown in fig. 7. The cell was placed in dark conditions at a temperature of about 25 ℃ and atmospheric humidity of about 50% with 85% of initial efficiency maintained after 30 days.
Example 4:
one with PEDOT: the preparation method of the perovskite solar cell with the PSS modified carbon electrode as the counter electrode comprises the following steps:
(1) Cleaning of FTO conductive substrates. As in example 1;
(2) Compact TiO 2 Is prepared by the following steps. As in example 1;
（3）TiO 2 preparation of a porous layer. As in example 1;
(4) And (3) preparing a perovskite light absorption layer. As in example 1;
(5) The preparation of the hole transport layer comprises the following specific processes: 1mL chlorobenzene, 72.3mg Spiro-OMeTAD, 28.8. Mu.L 4-tertbutylpheno, 17.5. Mu.L Li-TFSI (acetonitrile as solvent) at a concentration of 520mg/mL were thoroughly mixed. Taking 70 mu L of hole transport layer solution, spin-coating the solution onto a perovskite light absorption layer at a rotating speed of 4000rpm for 30s, and placing the solution in dry air in a dark place for 8 hours to obtain a hole transport layer with a thickness of 150 nm;
(6) And (3) preparing a carbon electrode layer. Commercial conductive carbon paste (original solvent is DBE, purchased from Borun New Material technology Co., ltd.) is coated on clean common glass (2 layers of 3M adhesive tape are adhered on a glass plate, a long strip-shaped carbon film with the width of 1cm is formed in the middle), a carbon wet film is obtained, and the carbon wet film is soaked in a solvent with PEDOT: putting PSS in absolute ethyl alcohol for 30 minutes (the volume ratio of PEDOT to PSS to absolute ethyl alcohol is 1:15), transferring the carbon film to a heating plate for heating at 70 ℃ for 10 minutes after the carbon film is fallen off, and obtaining a 30 mu m carbon electrode film;
(7) Cutting the carbon electrode film obtained in the step (6) into squares of 1cm x 1cm, and hot-pressing the squares on the hole transport layer prepared in the step (4), wherein the hot-pressing conditions are as follows: hot-pressing at 80deg.C under 1 MPa for 1min.
(8) The transparent conductive electrode and the carbon counter electrode were led out to obtain a perovskite solar cell, and performance test was performed, and the results are shown in fig. 8. The cell efficiency was measured to be 15.73%. Short circuit current, open circuit voltage, and fill factor are respectively: 21.76mA/cm 2 ，1.05V，0.69。
(9) The stability test results are shown in fig. 9. Placed under ambient dark conditions for 30 days (T.apprxeq.25℃, RH.apprxeq.50%), 96% of the initial efficiency was still maintained.
Claims (9)
1. PEDOT: the PSS modified carbon electrode is characterized by being obtained through the following process:
1) Blade coating commercial conductive carbon paste on common glass to form wet carbon film;
2) Immersing the wet carbon film in the solvent of PEDOT: soaking in absolute ethyl alcohol of PSS for 10-60 min, and PEDOT: the volume ratio of PSS to absolute ethyl alcohol is 1:1-20,
3) And (3) after the carbon film is removed from the glass, drying to obtain PEDOT: PSS-modified carbon electrode.
2. PEDOT according to claim 1: a PSS-modified carbon electrode characterized in that a 3M tape is stuck on a common glass to control the thickness of a wet carbon film when a carbon film is blade-coated, PEDOT: the volume ratio of PSS to absolute ethyl alcohol is 1:15, the soaking time of the carbon film in the ethyl alcohol is 1-30 minutes, and the drying temperature is 70 ℃.
3. PEDOT according to claim 1: PSS-modified carbon electrode, characterized in that the primary solvent in the commercial conductive carbon paste is DBE.
4. A PEDOT according to any of claims 1 to 3: the perovskite solar cell prepared from the PSS modified carbon electrode is characterized by sequentially comprising a conductive substrate, an electron transport layer, a perovskite light absorption layer and a carbon counter electrode, wherein the electron transport layer is formed by TiO (titanium dioxide) 2 Dense layer and TiO 2 A porous layer, wherein the perovskite light absorption layer is MAPbI 3 A film.
5. The perovskite solar cell of claim 4, wherein the conductive substrate is an FTO, ITO, or PET flexible substrate.
6. The perovskite solar cell of claim 4, wherein the electron transport layer is comprised of TiO 2 Dense layer and TiO 2 Porous layer composition, the TiO 2 The thickness of the compact layer is 5-50 nm, and TiO 2 The thickness of the porous layer is 100-500 nm, and TiO 2 The preparation process of the compact layer is as follows: spin-coating 0.15M n-butanol solution of titanium acetylacetonate on a conductive substrate, and drying at 120-130 ℃ to obtain the conductive substrate;
TiO 2 the porous layer was prepared as follows: commercial TiO to be purchased 2 Diluting the slurry 18NRT and absolute ethyl alcohol according to the volume ratio of 1 (5-7), and spin-coating on TiO 2 And (3) drying the compact layer at 120-130 ℃, and then sintering at 500 ℃ for 25-35 min to obtain the composite material.
7. The perovskite solar cell of claim 4, wherein the perovskite light absorbing layer is MAPbI 3 The thickness of the perovskite light absorption layer is 100-1000 nm, and the preparation process of the perovskite light absorption layer comprises the following steps: 0.461g of PbI 2 0.159g MAI is dissolved in a mixed solution of 0.2mL of DMF and 0.8mL of DMF and stirred fully to obtain perovskite precursor solution, and the perovskite precursor solution is coated on TiO in a spin-on manner 2 And (3) on the porous layer, obtaining a perovskite precursor film, and annealing at 100 ℃ to obtain the perovskite precursor film.
8. The perovskite solar cell of claim 4, wherein the carbon counter electrode is pressed on the perovskite layer by a pressure of 0.3-1.2 mpa, and the hot pressing temperature is 50-150 ℃.
9. The perovskite solar cell according to claim 4, wherein a Spiro-ome tad hole transport layer is further arranged between the perovskite light absorption layer and the carbon counter electrode, and the thickness of the hole transport layer is 50-300 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899504.1A CN113644208B (en) | 2021-08-06 | 2021-08-06 | PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899504.1A CN113644208B (en) | 2021-08-06 | 2021-08-06 | PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113644208A CN113644208A (en) | 2021-11-12 |
| CN113644208B true CN113644208B (en) | 2023-09-22 |
Family
ID=78419881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110899504.1A Active CN113644208B (en) | 2021-08-06 | 2021-08-06 | PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113644208B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701023A (en) * | 2015-01-21 | 2015-06-10 | 石家庄铁道大学 | Carbon electrode material of perovskite thin film solar cell and preparation method of carbon electrode material |
| CN106297946A (en) * | 2016-08-09 | 2017-01-04 | 重庆大学 | A kind of preparation method of carbon electrode based on ink print technique |
| CN108269918A (en) * | 2016-12-31 | 2018-07-10 | 中国科学院上海硅酸盐研究所 | Porous perovskite thin film, carbon pastes and the solar cell based on carbon electrode |
| CN108365108A (en) * | 2018-01-05 | 2018-08-03 | 南京邮电大学 | A kind of perovskite solar cell and preparation method thereof of p-type nano material embedded in carbon electrode |
| CN108408712A (en) * | 2018-03-26 | 2018-08-17 | 厦门大学 | A kind of preparation method and application of carbon black and its carbon electrode |
| CN109585054A (en) * | 2018-12-12 | 2019-04-05 | 新疆大学 | The dry conductive carbon paste of green solvent Shift Method is applied to perovskite solar battery |
| CN110299450A (en) * | 2018-03-23 | 2019-10-01 | 中国科学院物理研究所 | A kind of flexible, porous carbon is to electrode preparation method and Ca-Ti ore type solar battery |
| CN112614942A (en) * | 2021-01-08 | 2021-04-06 | 河南大学 | PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode |
-
2021
- 2021-08-06 CN CN202110899504.1A patent/CN113644208B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701023A (en) * | 2015-01-21 | 2015-06-10 | 石家庄铁道大学 | Carbon electrode material of perovskite thin film solar cell and preparation method of carbon electrode material |
| CN106297946A (en) * | 2016-08-09 | 2017-01-04 | 重庆大学 | A kind of preparation method of carbon electrode based on ink print technique |
| CN108269918A (en) * | 2016-12-31 | 2018-07-10 | 中国科学院上海硅酸盐研究所 | Porous perovskite thin film, carbon pastes and the solar cell based on carbon electrode |
| CN108365108A (en) * | 2018-01-05 | 2018-08-03 | 南京邮电大学 | A kind of perovskite solar cell and preparation method thereof of p-type nano material embedded in carbon electrode |
| CN110299450A (en) * | 2018-03-23 | 2019-10-01 | 中国科学院物理研究所 | A kind of flexible, porous carbon is to electrode preparation method and Ca-Ti ore type solar battery |
| CN108408712A (en) * | 2018-03-26 | 2018-08-17 | 厦门大学 | A kind of preparation method and application of carbon black and its carbon electrode |
| CN109585054A (en) * | 2018-12-12 | 2019-04-05 | 新疆大学 | The dry conductive carbon paste of green solvent Shift Method is applied to perovskite solar battery |
| CN112614942A (en) * | 2021-01-08 | 2021-04-06 | 河南大学 | PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode |
Non-Patent Citations (2)
| Title |
|---|
| "A low-temperature carbon electrode with good perovskite compatibility and high flexibility in carbon based perovskite solar cells";Shiyu Wang等;《ChemComm》;第55卷;2765-2768页 * |
| "Low-temperature carbon-based electrodes in perovskite solar cells";Dmitry Bogachuk等;《Energy & Environmental Science》;第13卷;3880-3916页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113644208A (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104157788B (en) | It is a kind of to be based on SnO2Perovskite thin film photovoltaic cell and preparation method thereof | |
| CN104505409B (en) | SnO2 porous structure perovskite photovoltaic cell and preparation method thereof | |
| CN101414663B (en) | Stacking polymer thin-film solar cell with parallel connection structure | |
| CN105336862A (en) | Integrated stack double-junction perovskite solar cell and preparation method thereof | |
| CN107359248B (en) | A kind of stabilization is without efficient organic solar batteries device of light bath and preparation method thereof | |
| CN104576932A (en) | Mesoscopic perovskite photovoltaic cell with tin-oxide electron-transporting layer and preparation method thereof | |
| CN105609640A (en) | Mechanically laminated perovskite solar cell and preparation method thereof | |
| CN101997085A (en) | Organic small molecule solar cell with inversion structure | |
| CN102299206A (en) | Heterojunction solar cell and manufacturing method thereof | |
| CN113193123B (en) | Double-interface-layer-modified efficient perovskite solar cell and preparation method thereof | |
| CN106601916B (en) | Organic solar batteries and preparation method thereof based on hetero-junctions cathode buffer layer | |
| CN111261783B (en) | Novel electron transport layer perovskite solar cell and preparation method thereof | |
| CN210092130U (en) | Perovskite solar cell based on hydrophobic coating | |
| CN112614942B (en) | PEG-modified carbon electrode, preparation method thereof and perovskite battery prepared by using PEG-modified carbon electrode | |
| CN113644208B (en) | PEDOT: PSS modified carbon electrode, preparation method thereof and perovskite battery prepared by using same | |
| CN111628087A (en) | Flexible solar cell capable of performing mechanoluminescence and preparation method thereof | |
| CN110085428A (en) | A kind of compound light anode of titanium dioxide/graphene and preparation method thereof | |
| CN204481033U (en) | A kind of SnO 2loose structure perovskite photovoltaic cell | |
| CN111129316A (en) | Carbon-based perovskite solar cell based on multifunctional composite current collector | |
| CN110165060B (en) | Preparation method of hole-free hole transport layer | |
| CN105826474A (en) | Outdoor parking management system with self-generating function | |
| CN105810824A (en) | Novel structured polymer solar cell | |
| CN112599680A (en) | Flexible perovskite solar cell based on polyimide substrate and preparation method thereof | |
| CN117615591A (en) | Inner packaging structure applied to underwater perovskite solar cell | |
| CN116666472A (en) | Large-area antimony selenide thin-film solar cell module and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |